Mixed ester amine polybasic acid compositions



Patented Sept. 25, 1951 UNITED STATES ATET OFFHCE MIXED ESTER AMINEPOLYBASIC ACID COMPOSITIONS poration of Delaware No Drawing. ApplicationJune 11, 1949, Serial No. 98,626

This invention relates to new and improved compositions adapted for thetreatment of emulsions of mineral oil and water, such as petroleumemulsions commonly encountered in the produc tion, handling and refiningof crude mineral oil, for the purpose of separating the oil from thewater. Also, the invention relates to compositions suitable for thetreatment of other waterin-oil types of emulsions wherein the emulsionsare produced artificially or naturally and the resolution of theemulsions presents a problem of recovery or disposal.

This application is a continuation-in-part of our copending applicationSerial Number 775,146, filed September 19, 1947.

Petroleum emulsions are, in general, of the water-in-oil type whereinthe oil acts as a continuous phase for the dispersal of finely dividedparticles of naturally occurring waters or brines. These emulsions areoften extremely stable and will not resolve on long standing. It is tobe understood that water-in-oil emulsions may occur artificiallyresulting from any one or more of numerous operations encountered invarious industries. The emulsions obtained from producing wells and fromthe bottom of crude oil storage tanks are commonly referred to as cutoil, emulsified oil, bottom settlings, and iiB. S.

One object of the invention is to provide a novel and useful compositionfor resolving emulsions of the character referred to into their component parts of oil and water or brine.

Another object of the invention is to provide a novel and usefulcomposition for desalting ofv able its use as a demulsifier or for suchuses where surface-active characteristics are necessary or desirable.Other objects will appear hereinafter.

The compositions provided in accordance with the present inventionconsist of a modified alkyd resin derived from the reaction of analkylol amine, a polybasic c'arboxy acid, and a mixed ester of apolyhydric alcohol, preferably a poly- 9 Claims. (01. 260 -22) 2alkylene glycol, of the kind obtained when a polyhydroxy organiccompound, e. g., a polyalkylene glycol or derivative thereof, unites toform mixed esters with two dissimilar carboxy acids, one being anunsaturated long chain acyclic carboxy acid containing at least 8 carbonatoms and the other being an unsaturated carbocyclic acidic resin typecarboxy acid, for instance, abietic acid. The modified alkyd resinresults from the condensation of an organic dibasic acid with the abovedescribed mixed ester and the reaction of an alkylol amine therewithwherein the modification is such that the resulting product iswater-wettable.

Polyalkylene glycols comprise a series of polymers having the generalformula HO (cnHznOCnl-Izn) 10H wherein n and a: are the same ordifferent whole numbers. Polyethylene glycols are currently available intechnical quantities and are offered in polymeric grades correspondingto molecular weights of 200, 300, 400, 600, 1000, 1500, 1540, 4000 and6000. Up to a molecular weight of 600, the materials all are viscous,light colored, somewhat hygroscopic liquids of low vapor pressure andare characterized by complete solubility in water and in many organicsolvents. Examples of the latter are aliphatic ketones and alcohols,glycol ethers, aliphatic esters and aromatic hydrocarbons. structurally,the polyethylene glycols are characterized by a large number of etherlinkages and two terminal hydroxyl groups so that they are heat stableand inert to many chemical agents. The higher molecular weightpolyethylene glycols are bland, odorless solids. The following are thephysical properties of the two polyethylene glycols which are ourpreferred reactants:

Polyethylene glycols Of the two dissimilar carboxy acids required foresterification, the one is preferably an unsaturated long chain acyclicor fatty type carboxy acid having at least 8 carbon atoms and not morethan 32 carbon atoms in the chain. This group of acids may also becalled unsaturated detergentforming acids. As examples of acyclic typeacids which we have found particularly suitable for our purposes we maymention: linolenic acid, linoleic acid, oleic acid, mixtures thereof,and other commonly available unsaturated long chain acyclic acids. Ofthese acids, those having a plurality of double bonds (e. g., linoleicacid and linolenic acid) may also be called drying oil acids. Especiallygood results have been obtained by the practice of the invention withblown esters derived from polyethylene glycols, and mixtures of dryingoil and non-drying (e. g., oleic acid) oil fatty acids, blown to a softviscous condition.

The other dissimilar type of carboxy acid required for our process is acarbocyclic carboxy acid of the terpene type, preferably a rosin acid.The most commonly available rosin acids are abietic acid and relatedderivatives derived from naval stores. Other acidic resins, e. g.,polymerized rosin, dehydrogenated rosin and cracked copals (for example,run Congo) may be employed.

The dissimilarity of these two types of carboxy acids is characterizedby the acyclic type being a long chain carboxy acid, whereas the rosintype is a carbocyclic carboxy acid of the terpene type. In the practiceof the invention the weight ratio of the acyclic carboxy acid to thecarbocyclic carboxy acid in the mixed ester is preferably within therange of 1:1 to 2:1, the lesser component always being in excess ofabout 30% of the total carboxy acids.

While any blend of the dissimilar acids can be prepared, our preferredmixture of dissimilar carboxy acids is readily obtainable as a naturallyoccurring mixture of dissimilar carboxy acids known in the trade as talloil. Tall oil is the liquid resin obtained in digesting wood to woodpulp in the paper industry. It is a dark brown, viscous liquidcontaining a crystalline sediment of abietic acid. From the results ofseveral investigators the following principal constituents of tall oilare indicated: resin acids 30-45%, fatty acids 45-60%, unsaponifiablematter 612 The unsaponifiable portion is a yellow viscous oil containinga waxy or pitchy material. The specifications of the particular grade oftall oil which we prefer to use is as follows:

Specific gravity (at 15.5 degrees C.) .9697 Acid number 164.0S'aponification number 173.6 Ester number 9.4

Percent moisture 0.0 Percent rosin 39.2 Percent fatty acids (bydifference 52.79

Percent linolenic acid 19.25

Percent linoleic acid 10.5

Percent oleic acid 23.04 Percent unsaponifiable 8.01 Iodine number148.83 Thiocyanogen-iodine number 91.1 Percent saturated fatty acidsnone Percent unsaturated fatty acids 100 Titer test degrees C. 5.5 Pourtest do 4.4 Cloud test do ll2.8

The preparation of the mixed dissimilar carboxy acid esters ofpolyalkylene glycols or their indicated equivalents is carried out inany of the well known conventional esterification procedures with orwithout catalysts. We prefer to carry out the esterification reaction bymixing the carboxy bodies and the polyhydroxy bodies in a suitablesolvent which is adaptable to aZQQQ P Q 4 distillation. It is to benoted that the use of a solvent is not essential but in some instancesits use may facilitate the reaction. Likewise, the use of catalysts suchas sulfuric acid and other acidic agents may facilitate the reaction.

The proportions of the polyhydric alcohols and carboxy acids and thereaction conditions are calculated to completely esterify the hydroxygroups and to remove by molecular dehydration all of the watercorresponding to the hydroxy groups of the polyhydric alcohol. Theresultant mixed ester in some cases may contain free carboxy groups (e.g., Examples II and III). In the latter cases, the alkylolamine canundergo an exchange equilibrium in situ and as the ester is formed,rather than stepwise as in the other examples.

In the practice of the invention, the alkylolamine modifies the resinousreaction products to prevent the formation of insoluble, infusibleresins. Satisfactory products may be secured by the use of alkylolamineswhich have been further condensed, molecularly dehydrated, polymerized,or converted to a more complex form by heating at elevated temperaturesin the presence or absence of suitable catalysts, or in the presence orabsence of acidic salts of multivalent metals (e. g., iron, aluminum,chromium and zinc) which form amphoteric hydroxides. The alkylolaminesreact with the completely esterified bodies in a manner similar to thereaction of glycerine in the making of superglycerinates from fattybodies.

Our preferred alkylolamine is triethanolamine which is a viscous andvery hygroscopic liquid which boils at 244 degrees C. at 50 mm. Acommercial product which is used for the purposes of the inventioncontains not more than 2.5% monoethanolamine and not more than 15%diethanolamine and not less than triethanolamine. The neutral equivalentof the commercial product will average about and is entirelysatisfactory for our purposes. Modification of triethanolamine can besecured by condensing in the presence or absence of zinc chloride and/orother multivalent metallic salts at an elevated temperature with orwithout molecular dehydration. There is little evidence available toindicate the nature and constitution of the material resulting from themolecular dehydration and/or polymerization of triethanolamine. From thefact that varying proportions of acidic salts such as zinc chlorideproduce different products, it may be deduced, however, that the metalactually forms a complex with the alkylolamine. This is evidenced by thefact that in one series of preparations 7% zinc chloride by weight oftriethanolamine gave a molecularly dehydrated amine product of differentcharacteristics from 1% zinc chloride. By acidic salts is meant thosesalts having an electronegative charge greater than the electronegativecharge of the 0H ion. For the most part these acidic salts are salts ofstrong acids, e. g., chlorides, nitrates, phosphates, sulfonates,sulfates and sulfamates.

Other examples of suitable primary, secondary and tertiary alkylolaminesfor these purposes are as follows: diethanolamine, octylethanolamine,cyclohexylethanolamine, diisopropanolamine, triisopropanolamine,2-amino-2-methyl-1-propanol and polyethanolamines. Recently there hasbecome available a commercial product satisfactory for our purposesdesignated as amine residue T (also called Polyamine T) which is a stilland sebacic acids, and 'homologues thereof, or

theiranhydrides.

In orderto illustrate specifically the new types of' materialscontemplated for use in accordance with the present invention, thefollowing examples are set forth below as being typical of productssuitable for use. It is to be understood, however, that we do notcon-fine'oursel'ves to the specific chemicals, or proportions thereof,set forth in these examples as it will be obvious that equivalents ofthese chemicals and other proportions may be used without departing fromthe spirit of the invention or the scope of the appended claims.

pproximately 3 poun of tal o l. 2 .0 pounds. of. pol ethylen lyco d gaof a suitabl hydroc rbo fr n uch s. 02 extracta h r ed. into t e pr s ngket The empe a u e s ra ed r th a tat o and at a ou 1.60. de r es. C. anaqu ous-l e di i l te be ns to form. heat ng s continued until a ot ofPounds. of aqueo s. s lat ha b co dens rom t e eac n T m mum temperaturreach d dur g th reaction is b ut. 240 d g e C. h react on a h n. oo edo 80 d grees C. and yields the mixed ester intermediate.

Forty-e ght hundred (48.00) pou ds. oi s t r edia e and 0 po nd o t ie hnoi u are harged in oth Pr e ing ket le an t t mp ra ure rai ed t 1' ege s- Q. d mai tained at ha po nt or three ours. The reaction prod ct. s,then pr m t y o l d. to abou .3 degrees. 0-. a this. poi t. 24 pou s ooh ha ic anhydr de is ha ge to the. t le n th t mpe a ur ai edl A aemper u elop ox inating 1. de rees C. an aqu ou dist llate is. securedHeat ng th agitation s continu d u til a to al of. 32 p unds oi aqu oudi ti ate een. e u d The actio ma is. the ooled to ahn oxiroa y 351 d gees at; this point. .5 g ll ns o asu ta le ydroca bon diluent is addedwith agitation The mass is fu t cool d and g llons oi i ro a are addedit stir in to ield the f n she product.

Approximately 2. 7.0 pounds o ta l o l ehnroximatel-rl l0. pounds of nolethrlehe lycol 400, approximatel 2. .0.0. hou ds of methano amine and2.50 gallons of a, suitable hydrocarbon diluent are charged into theprocessing kettle The temperature is gradually raised with agitationuntil an aqueous distillate begins to, form which should occur at.approximately 167 degrees C. The temperature is continued and graduallyelevated until a total of 3.7- gallons of an aqueous distillate has beensecured. In the laboratory the aqueous distillate was secured in threehours and at a maximum temperature of 23-11 degrees C.

This intermediate is cooled to approximately 140 degrees C. and 2480pounds of phthali-c ahhydride are added. The temperature is raisedimmediately and an aqueous distillate begins to form at about 1'75degrees C. The temperature is gradually raised until a. total offalgallons of so. i

de ees at wh point .2 0 gaiions of "nrco 01 are a ded. o mpl te t hatcAf add nal coolin t e materiai is pumped o e Ca and: 350. gallons of a.suitable hydrocarbon' diluent: are introduced into the kettle. The massisthen further cooled to about '75 degrees C., at

which point. approximately 125 gallons of acetone areadded to complete.the batch. After further cooling the material, is pumped over to yieldthe finished. product.

hundred 600)- pou s of ll oil p unds. oi: pol ethyl ne glycol 4.00,. 680pounds of diethanolamine and 120 gallons of a suitable hydrocarbondiluent are charged into the processing kettle. The temperature isgradbeen secured. T is. aqueous distillate was ser d in approximatelyfour hours at a maximum t mper re of 200 de rees C.

This. intermediate is cooled to approximately 1 19, degrees Q. and 24.00pounds of phthalic anby lhi are added together with 110 gallons of asuitable ydr car on. iluent- The temperature. is raised mmed at ly andan aqueous i tillate begins to form at about 165. degrees C.

The t mpe a ure is gradu y ra sed. until a total of 5 a lons of an queus di t lla ehas b en mate y 10 egrees 0-. and 385 allons of a sui ablehyd ocarbon luent ar t duc d into th ket le The s th n fu ther cooledto. abo

to. yield the fin h d Pr duc Six hundred ((3) parts o the. intermediatemixed ester as prepared in Example I, 150 parts of triethanolamin and1.20 pa -ts of a ecul rly dehydrated triethanolarnine are heated threehours at 1.15 de r es C. o e h a m is added 100 parts of; a suitablehydrocarbon diluent and 196. parts of maleic anhydride. The temperatureis gradually raised unt a tot of 6 parts of an aqueous-like distillatehas been secured.

" To the resulting pr du t; is adde 350 parts of a hydrocarbon diluentand 100 part o op py alcohol to yield th finished product.

Three hundred (300) parts of a fatty acid residue consisting chiefly ofoleic and linoleic acids,

300 parts of abietic acid, 200 parts of polyethylone glycol 200 and 200parts of a suitable hydrocarbon diluent are heated until a total of 24parts of aqueous-like distillate have been secured.

. Ihis intermediate mixed ester was. reacted with triethanolamine andphthalic anhydride in 7s o trnsoerenanelamine a e heated for t e a totalof 54 parts of an aqueous distillate had been secured. Three hundredtwenty-five (325) parts of a hydrocarbon fraction and 100 parts ofisopropyl alcohol were added with agitation to yield the finishedproduct.

EXAMPLE VII The directions of Example VI are followed with the exceptionof the replacement of 300 parts of triisopropanolamine with 300 parts ofamine residue T.

EXAMPLE VIII The directions of Example VI are followed with theexception of the replacement of 300 parts of triisopropanolamine with300 parts of a triethanolamine prepared by condensing and molecularlydehydrating in the presence of zinc chloride.

From the above examples it is to be noted that satisfactory products aresecured by manufacturing the intermediate mixed ester prior to thecondensation with polybasic acids to yield the modified alkyd resintype. Likewise, equally satisfactory products can be prepared byreacting the desired dissimilar carboxy compounds, the polyhydroxycompounds and the alkylolamine in one step.

The above examples are only a few of the many products which may beprepared according to the principles disclosed in the foregoingdiscussion. Various examples of the many products which answer thedescription herein made are contemplated; some may beoil soluble andothers water soluble, and in many instances they may possess dualsolubility to an appreciable extent. The suitability of any of theproducts for the breaking and resolving of any given emulsion canreadily be determined by conventional procedures. The products may beused as such for resolving emulsions of the water-in-oil type or theymay be admixed with other demulsifying reagents in varying ratios asrequired by the problem at hand. 7

The suitable hydrocarbon vehicle referred to in the examples is sulfurdioxide (S02) extract. This material is a by-product from the Edeleanuprocess of refining petroleum in which the undesirable fractions areremoved by extraction with liquid sulfur dioxide. After removal of thesulfur dioxide a mixture of hydrocarbons, substantially aromatic incharacter, remains which is designated in the trade as S02 extract.Examples of other suitable hydrocarbon vehicles are toluene, xylene, gasoil, diesel fuel, bunker fuel and coal tar solvents. The above cited examples of solvents are adaptable to 'azeotropic distillation as wouldalso be any other solvent which is immiscible with water, miscible withthe reacting mass and has a boiling point or boiling range in excess ofthe boiling point of water.

For the purpose of the present invention the preferred products arethose in which 1 mol of the total ester (both hydroxy groups of thepolyhydric alcohol esterified with mixed acids) is modified with frommol to 3 mols of alkanolamine and 1 mol of the resultantalkylolaminemodified ester is condensed with from A mol to 3 mols of thepolybasic carboxy acid.

The improved demulsifying reagents prepared inaccordance with thepresent invention are preferably used in the proportion of one part ofreagent to from 2,000 to 30,000 parts of emulsion either by adding theconcentrated product directly to the emulsion or after diluting with asuitable vehicle in the customary manner.

The invention is hereby claimed as follows:

1. A composition of matter comprising a modified alkyd resin derivedfrom the reaction of a polycarboxy organic acid, a mixed ester, and analkylol amine, said mixed ester resulting from the reaction of apolyethylene glycol having a molecular weight within the range from 200to 600 and a mixture of at least two dissimilar unsaturated monocarboxyorganic acids wherein at least one of said acids is a carbocyclicnatural resin acid and another is an acyclic monocarboxy acid having atleast 8 and not more than 32 carbon atoms in the chain, the weight ratioof said acyclic monocarboxy acid to said carbocyclic monocarboxy acid inthe mixed ester being within the range of 1:1 to 2:1 and the lesser ofsaid monocarboxy acids component always being in excess of about 30% ofthe total monocarboxy acids, the quantity of said unsaturatedmonocarboxy acids being sufiicient to esterify completely the hydroxylgroups of said polyethylene glycol, the proportions of said reactantscorresponding to 1 mo1 of total mixed ester per A; mol to 3 mols ofalkylol amine and 1 mol of the resultant alkylol amine-modified esterper mol to 3 mols of said polycarboxy organic acid, said reaction beingeffected with the elimination of water at a temperature of r at least C.to produce a water wettable product.

2. A composition of matter comprising a modified alkyd resin derivedfrom the reaction of a polycarboxy organic acid, a polyethylene glycolhaving a molecular weight within the range of from 200 to 600,triethanolamine and tall oil, the proportions of said polyethyleneglycol and said tall oil being calculated to completely esterify thehydroxyl groups of said polyethylene glycol and the proportionscorresponding to 1 mol of the resultant mixed ester per M mol to 3 molsof triethanolamine and 1 mol of the resultant alkylol amine-modifiedester per to 3 mols of said polycarboxy organic acid, said reactionbeing effected with the elimination of water at a temerature of at least165 C. to produce a water wettable product.

3. A composition as claimed in claim 1 wherein the polycarboxy organicacid is phthalic anhydride.

4. A composition as claimed in claim 1 wherein the polycarboxy organicacid is maleic anhydride.

5. A composition as claimed in claim 1 wherein the alkylol amine istriethanolamine.

6. A composition as claimed in claim 1 wherein the alkylol amine isdiethanolamine.

7. A composition as claimed in claim 1 wherein the alkylolamine istriisopropanolamine.

8. A composition of matter comprising a modified alkyd resin derivedfrom the reaction of a polyethylene glycol having an average molecularweight within the range from 200 to 600, phthalic anhydride,triethanolamine and tall oil, the proportions of said polyethyleneglycol and the monocarboxy acids present in said tall oil beingcalculated to completely esterify the hydroxyl groups of saidpolyethylene glycol and the proportions corresponding to 1 mol of theresultant mixed ester per mol to 3 mols of triethanolamine and 1 mol ofthe resultant triethanolaminemodified ester per A mo1 to 3 mols ofphthalic 9 I anhydride, said reaction being effected with theelimination of Water at a temperature of at least 165 C. to produce awater Wettable product.

9. A composition of matter comprising a modified alkyd resin derivedfrom the reaction of a polyethylene glycol having an average molecularweight of about 400, phthalic anhydride, triethanolamine and tall oil,the proportions of said polyethylene glycol and the monocarboxy acidspresent in said tall oil being calculated to completely esterify thehydroxyl groups of said polyethylene glycol and the proportionscorresponding to 1 mol of the resultant mixed ester per mol to 3 mols oftriethanolamine and 1 mol of the resultant triethanolamine-modifiedester per mol to 3 mols of phthalic anhydride, said reaction beingeffected with the elimination of 10 water at a temperature of at least165 C. to produce a water wettable product.

WILLARD H. KIRKPATRICK. EARL T. KOCI-IER.

REFERENCES CITED The following references are of record in the NumberName Date 2,106,522 Ellis Jan. 25, 1938 2,214,784 Wayne Sept. 17, 19402,296,600 De Groote et a1. Sept. 22, 19 1-2v FOREIGN PATENTS NumberCountry Date 378,596 Great Britain Aug. 18, 1932

1. A COMPOSITION OF MATTER COMPRISING A MODIFIED ALKYD RESIN DERIVEDFROM THE REACTION OF A POLYCARBOXY ORGANIC ACID, A MIXED ESTER, AND ANALKYLOL AMINE, SAID MIXED ESTER RESULTING FROM THE REACTION OF APOLYETHYLENE GLYCOL HAVING A MOLECULAR WEIGHT WITHIN THE RANGE FROM 200TO 600 AND A MIXTURE OF AT LEAST TWO DISSIMILAR UNSATURATED MONOCARBOXYORGANIC ACIDS WHEREIN AT LEAST ONE OF SAID ACIDS IS A CARBOCYCLICNATURAL RESIN ACID AND ANOTHER IS AN ACYCLIC MONOCARBOXY ACID HAVING ATLEAST 8 AND NOT MORE THAN 32 CARBON ATOMS IN THE CHAIN, THE WEIGHT RATIOOF SAID ACYCLIC MONOCARBOXY ACID TO SAID CARBOCYCLIC MONOCARBOXY ACID INTHE MIXED ESTER BEING WITHIN THE RANGE OF 1:1 TO 2:1 AND THE LESSER OFSAID MONOCARBOXY ACIDS COMPONENT ALWAYS BEING IN EXCESS OF ABOUT 30% OFTHE TOTAL MONOCARBOXY ACIDS, THE QUANTITY OF SAID UNSATURATEDMONOCARBOXY ACIDS BEING SUFFICIENT TO ESTERIFY COMPLETELY THE HYDROXYLGROUPS OF SAID POLYETHYLENE GLYCOL, THE PROPORTIONS OF SAID REACTANTSCORRESPONDING TO 1 MOL OF TOTAL MIXED ESTER PER 1/3 MOL TO 3 MOL OFALKYLOL AMINE AND 1 MOL OF THE RESULTANT ALKYLOL AMINE-MODIFIED ESTERPER 1/2 MOL TO 3 MOLS OF SAID POLYCARBOXY ORGANIC ACID, SAID REACTIONBEING EFFECTED WITH THE ELIMINATION OF WATER AT A TEMPERATURE OF ATLEAST 165* C. TO PRODUCE A WATER WETTABLE PRODUCT.